Risk e Learning

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Risk e Learning Metals Remediation May 14,
2003 200 400 pm EDT
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Biosurfactants Applications for Metal
Remediation
Raina M. Maier Mark L. Brusseau
Janick F. Artiola Julia W. Neilson
Department of Soil, Water and Environmental
Science The University of Arizona, Tucson, AZ
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Applications for microbial surfactants

• Production of fine chemicals
• Bioremediation
• biodegradation of organics
• biodegradation in the presence of toxic metals
• removal of organics by flushing
• removal of metals by flushing
• Biological control
• Antibiotic facilitator

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Examples
surfactin
rhamnolipid
surfactant monomer
micelle (d 5 nm)
bilayer
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vesicle (d 20 to 400 nm)
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Examples (cont.)
carboxymethyl-beta-cyclodextrin
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Conceptual Diagram
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Rhamnolipid complexation of various metals
Cyclodextrin
Ochoa-Loza et al., 2000
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Environmental Compatibility vs. Strength of Metal
Complexation
Maier and Soberon-Chavez, 2000
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• Anticipated problems in application
• interference by naturally occurring metals
• interference by naturally occurring organic
  ligands
• interference from sorption
• metal aging

Ca2
K
Mg2
Humic acids
Fulvic acids
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Rhamnolipid and Fulvic Acid Complexation with
Metals
SFA soil derived fulvic acid WFA water
derived fulvic acid
1 Adhikari and Hazra (1972) 5 Schnitzer and
Skinner (1966, 1967) 2 Cheam and Gamble (1974)
6 Schnitzer and Khan (1972) 3 Saar and Weber
(1980) 7 Schuman and Cromer (1979) 4
Schnitzer and Hansen (1970)
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Soil properties that impact rhamnolipid
sorption Clays illite gt kaolinite gt
Ca-montmorillinite Metal oxides hematite
(Fe2O3) gt MnO2 gt gibbsite (AlOH3) Organic
matter humic acid
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Rhamnolipid-enhanced removal of cadmium from soil
aged one month no electrolyte pretreatment
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Torrens et al., 1998
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Metal removal efficiency from freshly
contaminated soils ranges from 50 to 100
depending on the soil type. Aged soils are more
problematic.
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Removal of Aged Soil-Bound Metals 3 examples
Post Office Site (2000 mg Pb/Kg soil)
Contaminant metals present TCLP Pb 2000
mg/Kg Pb 12.5 mg/L Cu 21,000 mg/Kg Zn 26.7
mg/L Zn 2,500 mg/Kg Cu 33.3 mg/L Fe 150,000
mg/Kg
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Coeur dAlene Soil- mining Soluble, Exchangeable,
Oxide-bound and residual Camp Navajo Soil
army depot Soluble, Exchangeable, Carbonate-bound
and residual

• Soil Washing Agents
• 10mM Rhamnolipid
• 50mM Ca(NO3)2
• 10mM KNO3

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Neilson et al., 2003
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A comparison of Rhamnolipid and Cyclodextrin
Coeur dAlene Soil Soluble, Exchangeable,
Oxide-bound and residual Camp Navajo
Soil Soluble, Exchangeable, Carbonate-bound and
residual
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Neilson et al., 2003
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Biosurfactant application to facilitate
biodegradation in co-contaminated sites
Rhamnolipid-facilitated biodegradation of
phenanthrene in Brazito soil contaminated with
cadmium
17Maslin and Maier, 2000
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Rhamnolipid-facilitated biodegradation of
phenanthrene in Gila soil contaminated with
cadmium
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Conclusions

• Biosurfactants are an example of an
  environmentally
• compatible agent with potential for remediation
  of
• metals.
• Likely we can improve on performance by looking
  at
• other natural products including
• other biosurfactants
• siderophores
• metallothioneins

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16s rDNA phylogenetic tree of biosurfactant-produc
ing microbes
Ability to produce biosurfactants is widespread!
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Bodour et al., 2003
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Physical-chemical properties of surfactants vary
greatly resulting in different potential
applications.

• This is true for different types of
  biosurfactants
• It is also true within a biosurfactant type.

ATCC 9027 IGB83
158 m-Rhl m-Rhl d-Rhl
Rhl-methyl esters
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References Bodour, A.A. and R.M. Maier.
Distribution of biosurfactant-producing
microorganisms in undisturbed and contaminated
arid southwestern soils. Appl. Environ.
Microbiol., 69(6)xxx-xxx. Sandrin, T.R. and R.M.
Maier. Impact of metals on the biodegradation of
organic pollutants. J. Environ. Health Perspec.,
in press. Neilson, J.W., J.F. Artiola, and R.M.
Maier. Characterization of lead removal from
contaminated soils by nontoxic soil-washing
agents. J. Env. Qual., 32xxx-xxx. Maier,
R.M. Biosurfactants Evolution and Diversity.
Adv. Appl. Microbiol., in press. Bodour, A.A.,
and R.M. Maier. 2002. Biosurfactants types,
screening methods, and applications. Chapter in
Encyclopedia of Environmental Microbiology
(G. Bitton, ed.) John Wiley and Sons, pp.
750-770. Jordan, F.L., M. Robin-Abbott, R.M.
Maier, and E.P. Glenn. 2002. A comparison of
chelator-facilitated metal uptake by a halophyte
and a glycophyte. Environ. Toxicol. Chem.,
212698-2704. Maier, R.M., J.W. Neilson,
J.F.Artiola, F.L. Jordan, E.P. Glenn, and S.M.
Descher. 2001. Remediation of
metal-contaminated soil and sludge using
biosurfactant technology. Internat. J.
Occupational Med. Environ. Health,
14241-248. Ochoa-Loza, F.J., J.F. Artiola, and
R.M. Maier. 2001. Stability constants for the
complexation of various metals with a rhamnolipid
biosurfactant. J. Env. Qual.
30479-485. Sandrin, T. R., A.M. Chech, and R.M.
Maier. 2000. A rhamnolipid biosurfactant
reduces cadmium toxicity during naphthalene
biodegradation. Appl. Environ. Microbiol.
664585-4588. Maslin, P. and R.M. Maier. 2000.
Rhamnolipid-enhanced mineralization of
phenanthrene in organic-metal co-contaminated
soils. Biorem. J. 4295- 308. Maier, R.M.
and G. Soberon-Chavez. 2000. Pseudomonas
aeruginosa rhamnolipids biosynthesis and
potential environmental applications. Appl.
Microbiol. Biotechnol. 54625-633. Bodour,
A.A., and R.M. Miller-Maier. 1998. Application
of a modified drop-collapse technique for
surfactant quantitation and screening of
biosurfactant-producing microorganisms. J.
Microbiol. Methods, 32372-280. Torrens, J.L.,
D.C. Herman, and R.M. Miller-Maier. 1998.
Biosurfactant (rhamnolipid) sorption and the
impact on rhamnolipid-facilitated removal
of cadmium from various soils. Environ. Sci.
Technol., 32776-781. Herman, D.C., Y. Zhang,
and R.M. Miller. 1997. Rhamnolipid
(biosurfactant) effects on cell aggregation and
biodegradation of residual hexadecane under
saturated flow conditions. Appl. Environ.
Microbiol. 633622-3627. Wild, M., A.D. Caro,
A.L. Hernandez, R.M. Miller, and G.
Soberon-Chavez. 1997. Selection and partial
characterization of a Pseudomonas
aeruginosa monorhamnolipid deficient mutant.
FEMS Microbiol. Lett. 153279-285. Herman,
D.C., J.F. Artiola, and R.M. Miller. 1995.
Removal of cadmium, lead, and zinc from soil by a
rhamnolipid biosurfactant. Environmental
Science and Technology. 292280-2285. Champion,
J.T., J.C. Gilkey, H. Lamparski, J. Retterer, and
R.M. Miller. 1995. Electron microscopy of
rhamnolipid (biosurfactant) morphology
effects of ph, cadmium and octadecane. J.
Colloid Interface Sci. 170569-574. Miller, R.M.
Biosurfactant-facilitated remediation of
metal-contaminated soils. 1995. Environ. Health
Perspec., 103 (Suppl 1)59-62. Tan, H., J.T.
Champion, J.F. Artiola, M.L. Brusseau, and R.M.
Miller. 1994. Complexation of cadmium by a
rhamnolipid biosurfactant. Environ. Sci.
Technol., 282402-2406.
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Green Engineering
Harry R. Compton Environmental Engineer U.S. EPA
- ERT
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Mine Sites

• Lack of vegetation result of
• __ Fertility
• __ Soil physical properties
• __ Acidity
• __ Metal toxicities
• __ Salts

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Goals of remediation

• Reduce bioavailability of contaminant in place
• Rebuild soil or build new soil
• Restore soil function
• Sustain plant growth
• Sustain soil fertility
• Establish native plant ecosystem

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Why use wastes?

• Different wastes can be used to remedy a number
  of factors that may potentially contribute to a
  soils inability to support a vegetative cover.
• -- pH
• -- soil fertility
• -- soil physical properties, and
• -- potentially toxic concentrations of trace
  metals
• By combining different materials together, and
  applying to the soils in-place, soil problems can
  be corrected.
• -- lower costs
• -- recycling wastes

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Biosolids
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Metals in Biosolids

• Regulatory limit
• (pollutant concentration limits)
• Cadmium
• 39 mg kg
• Lead
• 300 mg kg
• Copper
• 1500 mg kg
• Zinc
• 2800 mg kg

• National Means
• (1990 national sewage sludge survey)
• Cadmium
• 7 mg kg
• Lead
• 134 mg kg
• Copper
• 741 mg kg
• Zinc
• 1202 mg kg

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Scientific basis of treatments

• Biosolids/compost add
• nutrients
• organic matter
• metal complexing ability
• Wood ash/waste lime add
• pH adjustment
• adhesive properties
• nutrients
• Wood waste/other C-rich residuals
• limits N availability
• adds bulk
• physical soil benefits

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Bunker Hill - wetland restoration

• Lead 30,000 mg kg-1
• Zinc 15,000 mg kg-1
• Cadmium 100 mg kg-1

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Waterfowl

• Use Lateral Lakes wetlands as feeding, nesting
  area
• Dive for roots and tubers
• 20 of diet is sediment
• Acute Pb poisoning
• 100 sq mile area is Pb enriched

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Coeur dAlene Wetlands1998- 2001
1998
2001
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Wetland - Plant lead(mg kg-1)
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Other metals
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Pb Speciation
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Summary of Desorption

• Biosolids significantly increased hysteresis
• For a site hystersis was related to rate of
  application
• The effect of biosolids application on hystersis
  was also apparent on the inorganic fraction of
  the samples
• Removal of organic carbon and the Fe/Mn fraction
  from the samples removed the difference caused by
  biosolids

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Summary Adsorption/Desorption

• Biosolids increased the soils ability to adsorb
  and retain Cd
• These changes are apparent in the inorganic
  fraction of the samples
• Removal of organic carbon and the Fe/Mn fraction
  from the samples removes the difference caused by
  biosolids addition
• Thus the Fe/Mn fraction of the biosolids is an
  important component of the change in
  adsorption/desorption

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